Calixarenes crown ether derivatives

Channel-like architectures are formed in the mesophase given by complexes of long chain crown ether derivatives [8.196a,b] and long-chain calixarene derivatives display columnar liquid-crystalline arrangements [8.196c]. Self-assembled tubular structures based on cyclic peptide components have been described [8.186]. 

Conformational fixing of calix[8]arenes is more difficult than in the case of the smaller calixarenes. Even bis-crown ether derivatives such as 1,3-5,7-calix[8]bis-... 

After the success ofVM-based ISEs, a number of synthetic ionophores were applied for the developments of respective ISEs. For alkali metal ions, crown-ether derivatives and calixarene derivatives were employed... 

Experimental work on new partitioning techniques is performed in the fiiamework of two projects. The first one has the objective to develop processes for the separation of minor actinides from very acidic aqueous solutions containing high level waste without the generation of secondary solid waste. In the second one, extractants selective to strontium, actinides -I- lanthanides, and actinides only such as calixarene and crown ether derivatives will be synthesised. The extracting properties of these compounds will be determined experimentally and modelled with molecular mechanics and molecular dynamics simulations. 

Many other cyclic and noncyclic organic carriers with remarkable ion selectivities have been used successfiilly as active hosts of various liquid membrane electrodes. These include the 14-crown-4-ether for lithium (30) 16-crown-5 derivatives for sodium bis-benzo-18-crown-6 ether for cesium the ionophore ETH 1001 [(R,R)-AA -bisd l-ethoxycarbonyl)undecyl-A,yVl-4,5-tctramcthyl-3,6-dioxaoctancdiamide] for calcium the natural macrocyclics nonactin and monensin for ammonia and sodium (31), respectively the ionophore ETH 1117 for magnesium calixarene derivatives for sodium (32) and macrocyclic thioethers for mercury and silver (33). 

Polymer supported xanthene derivatives have been used in the solid phase synthesis of 1-aminophosphinic acids, RCH(NH2)PH(0)0H, <%TL1647> and of C-terminal peptide amides <96JOC6326>. Xanthene units also feature in crown ethers <96JCS(P2)2091>, calixarenes <96JOC5670> and in a flexible template for a P-sheet nucleator <96JOC7408>. 

With the alkynyl functionality greater than two, starbust type complexes are obtained, as derived, for example, from 1,3,5-trialkynylbenzenes 85 or -triazines,86 1,1,2,2-tetraalkynylethenes,85 or bis(l,2-dialkynyl)phenylene-bridged crown ethers or calixarenes. ... 

Supramolecnlar derivatives containing crown ether [228], calixarenes [264, 265] or dendrimers [267, 279] have been synthesized with the precursors shown in Table 4.10. Fullerene-flavonoid [268] or the fuUerene glycoconjugate [258] derived from 237 and 235, respectively, are expected to show biological activity. 

Calixarene derivatives involving crown ethers like 233 exhibit complexation ofalkali or ammonium cations typical of crown ethers that is especially effective in the partial cone conformation [26]. By a proper functionalization selective synthetic receptors for specific hosts have been developed. For instance, two 2,4-diaminotriazine groups at diametrical positions of the upper rim of a... 

Calixarene crown-6 compounds, which are neutral extractants like crown ethers, are able to coextract technetium with cesium. Tests carried out with several calix-arene-crown ethers (MC7, MC8, MC14, BC2, BC5, BC8, and BC10) show that the extraction of technetium, present in the aqueous phase at a concentration 10 5 M, is enhanced as the cesium concentration in the aqueous phase increases from 10 5 to 10-2 M. As expected, an increase of nitrate concentration prevents pertechnetate extraction in competition with nitrate anion. The extraction of technetium is only appreciable when the nitric acid does not exceed 1 M. Distribution ratios DCs (close to 8) are comparable for the various calixarenes. However, a decrease of extraction is observed for naphtho derivatives.88 89... 

The selectivities of Cs+ ISEs based on dibenzo-18-crown-6 derivatives <1986FZA241> or 2,3-benzoquinone 15-crown-5 ethers <1996AN127> are of limited interest, because they are not dissimilar to those found with iono-phore-free ion-exchanger ISEs < 1977ANA399>. Nowadays, the best Cs+ selectivities are obtained by using calixarene-derived crown ethers . 

Calixarenes were developed later than crown ethers and cyclodextrins but have stillbeen extensively researched. Macrocycles of calix[n]arenes are constructed by linking a number of phenol residues via methylene moieties (Fig. 2.16). Like crown ethers, the name calixarene reflects the structures of these molecules, since a calix is a chalice. Calixarenes with various cavity sizes have been designed, each of which has conformation isomers, and their phenolic hydroxyl groups are often modified. These structural characteristics allow us to create calixarene derivatives with various structural modifications. 

In addition to crown-ethers, calix[4]resorcinarenes 19 have also been used as head groups to obtain azobenzene amphipbiles with sufficient photo-isomerization in LBK films. For this purpose, azobenzene moieties have been tethered to the lower rim of the crown conformer of the calixarene. O-octacarboxymethoxylated calix[4]resorcinarenes 19 (X = CH2-COOH) display efficient trans to cis photoisomerizability in densely packed mono-layers on a water surface, in LBK films, and in surface-adsorbed monolayers, whereas the noncarboxymetylated 19 (X = H) derivative gives films that are too densely packed. However, the aggregation is already suppressed efficiently compared to the azobenzene derivative without calixaren. ... 

Only few investigations have been published on the gas-phase ion chemistry of host-guest complexes of calixarenes. With the advent of ESI mass spectrometry, especially when combined with ion-trap and FT-ICR mass spectrometry, this field has started to be developed. Binding selectivities of alkali metal ions to cahxarene-based crown ethers and open-chain ethers have been studied , the inclusion of neutral guests into the protonated resorcarene-based cavitand hosts by gas-phase ion-molecule reactions with amines have been studied and the formation of capsules from various calixarene tetraether derivatives and alkylammonium ions as ionic guests (notably enabling their detection by mass spectrometry) have been described recently . ... 

Isoaromatization of dienone macrocycles afforded Horning-crown macro-cycles - flexible macrocycles bearing structural elements reminiscent of those found in both calixarenes and crown ethers. In some cases the Horning-crown macrocycles exhibited solvent-dependent and switchable conformations. For macrocycles with the same short linker, self-complementarity was observed, and dimers tended to crystallize as solvates or inclusion compounds. This tendency was suppressed with longer linkers and in some Horning-crowns derived from trapezoidal macrocycles. These properties suggest potential applications in analysis, separation and detection (Figure 6.8). ... 

The crown ether, 18-crown-6 [34—36], [2.2.2]-cryptand [37], and calixarene derivatives of hydroxamic acids have also been used for extraction of U(VI) [38]. 

The two calix[4]arenes, 24 and 26, are examples of useful derivatives the former binds lanthanides to form luminescent complexes, the latter, prepared from compound 25, is water soluble and crystallizes in a variety of forms, from laminates to nanospheres. Other derivatives are to be found in the literature. Simple derivatives, such as the O-alkyl compounds, are used as a basis for upper rim functionalization treatment of these compounds with nitric acid replaces the upper f-butyl groups with nitrates. Nitrocalixarenes can be reduced to the corresponding amines to generate a platform for further extension of the cavity and have been used to bind metals or small molecules. Oxa- and azacalix[3]arenes represent crown ether-calixarene hybrids and have binding modes reminiscent of both classes of molecules. Many alternative upper rim substituents can be introduced and, in the case of the azacalixarenes, the /V-substituent can easily be varied. 

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